Protected aminofunctionalized polymerization initiators and methods of making and using same

a polymerization initiator and functional technology, applied in the field of polymerization initiators, can solve the problems of reducing the amount of 1,2-microstructure in the resultant polymer, etc., and achieving the effect of commercial production of functionalized polymers at 78° c. and thf solvents

Inactive Publication Date: 2005-05-10
FMC CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0012]The present invention relates to protected amine functionalized initiators and processes for making and using the same to prepare amine functionalized polymers. The initiators of the invention include a tertiary amine functionality. The amine functionality includes two protecting groups, which may be the same or different. When the protecting groups are different, the groups are selected so as to have differential stability under specified deprotection conditions. Accordingly one of the protecting groups can be selectively removed without removing the other protecting group. In this manner, secondary amine functionalized polymers can be readily prepared.
[0019]R2 can be the same as R1, with the proviso that when R1 is methyl, R2 is not C1-C4 alkyl, or R2 can be different from R1, in which case R2 is selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, and substituted heterocycloalkyl, with the proviso that when R2 is not the same as R1, then R2 is more stable under conditions used to remove R1,
[0022]These initiators can be treated with organometallic compounds, containing Mg, Zn, B, Al, and the like, to potentially afford higher solubility of the initiators in hydrocarbon solutions and / or living polymer stabilization. Other additives, such as those disclosed in copending U.S. Ser. No. 09 / 149,952, filed Sep. 9, 1998, and U.S. Ser. No. 09 / 512,494, filed Feb. 24, 2000, the entire disclosure of each of which is hereby incorporated by reference, can also be used to improve initiator solubility and / or living polymer stabilization.

Problems solved by technology

Further, this dilithium approach can only afford telechelic polymers with the same functional group on each end of the polymer chain.
The addition of an ethereal co-solvent does increase the solubility of these initiators; however, this also increases the amount of 1,2-microstructure in the resultant polymer.
However, the reaction conditions (−78° C., THF solvent) were not practical for commercial production of these functionalized polymers.

Method used

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  • Protected aminofunctionalized polymerization initiators and methods of making and using same
  • Protected aminofunctionalized polymerization initiators and methods of making and using same
  • Protected aminofunctionalized polymerization initiators and methods of making and using same

Examples

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Effect test

example 1

Preparation of Initiator Precursor 3-[(N-benzyl-N-methyl)amino]-1-propylchloride

[0135]To a stirred suspension of K2CO3 (200 g, 1.5 mole) in cyclohexane 200 mL and 1-bromo-3-chloropropane (“BCP”) (540 g, 3.4 mole) was added dropwise over a period of 1 hour at 20° C. benzylmethyl amine (272 g, 2.24 mole). After complete addition the reaction was allowed to stir for an additional 20 hours. The crude reaction mixture was filtered and then washed with saturated NaCl (3×100 mL). The organic phase was extracted with 3N HCl (3×100 mL). The resulting aqueous phase, containing the desired product as the hydrochloric salt, was washed with hexanes (3×100 mL) to remove any residual BCP. The aqueous phase was subsequently basified with 50 wt % NaOH and extracted with cyclohexane (3×100 mL). After solvent removal 220 g (50% yield) of the title compound was isolated as a yellow oil.

example 2

Preparation of 3-[(N-benzyl-N-methyl)amino]-1-propyllithium

[0136]To a 500 ml Morton / cleave flask reactor under argon atmosphere was added lithium powder (13.32 g, 1.92 mole) and 141 grams of cyclohexane. To a constant addition funnel was added 3-[(N-benzyl-N-methyl)amino]-1-propylchloride (70.93 g, 0.34 mol) and 83.3 grams cyclohexane. Immediately before beginning the addition, the lithium metal mixture was heated to 53° C. using a heating mantel. Dropwise addition of the feed solution was performed while maintaining the reaction temperature at 50° C. A cooling bath of hexane, to which dry ice was added periodically, was employed to maintain a reaction temperature between 48° to 51° C. The total addition time was 1.22 hours with an average stirring rpm of 925. The reaction mixture was stirred at least one hour after the feed was completed. This mixture was then pumped through a ⅜″ teflon tube to a pressure filter that contained about 10 grams of filter aid and filtered under an argo...

example 3

Preparation of Initiator Precursor 3-[(N,N-dibenzylamino]-1-propylchloride

[0137]To a stirred suspension of K2CO3 (200 g, 1.5 mole) in cyclohexane 200 mL and 1-bromo-3-chloropropane (540 gms, 3.4 mole) is added dropwise over a period of 1 h at 20° C. dibenzyl amine (442 g, 2.24 mole). After complete addition the reaction is allowed to stir for an additional 20 h. The crude reaction mixture is filtered and then washed with saturated NaCl (3×100 mL). The organic phase is extracted with 3N HCl (3×100 mL). The resulting aqueous phase, containing the desired product as the hydrochloric salt, is washed with hexanes (3×100 mL) to remove any residual BCP. The aqueous phase is subsequently basified with 50 wt % NaOH and extracted with cyclohexane (3×100 mL). After solvent removal 324 g (53% yield) of the title compound was isolated as a yellow oil.

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Abstract

Anionic polymerization initiators useful in the preparation of polymers having a protected amine functional group. The amine functionality includes a first protecting group, which can be aralkyl, methyl, allyl or tertiary alkyl group. The other of the amine protecting groups can be the same as the first protecting group. Alternatively, the second protecting group can be different from the first protecting group, in which case it is selected to have differential stability to agents used to remove the aralkyl, methyl, allyl or tertiary alkyl protecting group.

Description

CROSS REFERENCE TO RELATED APPLICATIONS[0001]This application is a divisional of U.S. application Ser. No. 09 / 655,528, filed Sep. 19, 2000 now U.S. Pat. No. 6,610,859, which is a continuation-in-part of U.S. application Ser. No. 09 / 256,737, filed Feb. 24, 1999 now U.S. Pat. No. 6,121,474, the disclosures of which are incorporated by reference herein in their entireties.FIELD OF THE INVENTION[0002]The present invention relates to polymerization initiators, and more particularly to anionic polymerization initiators having protected amine functionality, as well as processes for making and using the same and polymers prepared using the initiators.BACKGROUND OF THE INVENTION[0003]Olefinic containing monomers can be polymerized using organo-alkali metal initiators, such as butyllithium. The resultant intermediate polymer contains an active alkali metal end group, which can be subsequently reacted with a suitable protonating, functionalizing, or coupling or linking agent to replace the alk...

Claims

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Application Information

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Patent Type & Authority Patents(United States)
IPC IPC(8): C07F1/00C07F1/02C08F36/04C08F4/46C08C19/00C08F8/00C08F8/42C08F4/00C08C19/44C08F36/00C08F257/00C08F279/02C08F279/00C08F257/02C07F1/04C07F1/06C08F4/48C08F8/30
CPCC07F1/02C08C19/44C08F4/46C08F8/42C08F36/04C08F279/02C08F257/02Y02P20/55
Inventor BROCKMANN, THORSTEN WERNERHALL, RANDY W.
Owner FMC CORP
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